Process for the polymerization of diolefins



Patented Mar. 20, i945 aan,

PROCESS FOR THE POLYMERIZATIDN F DIOLEFINS Walter Afschulze 'and william N. Axe, Bartlesville, Okla., assignors to Phillips Petroleum Company, a corporation of Delaware Application January 24, 1942, Serial No. 428,122

16 Claims.

The present invention relates to a new process for the production of polymers from butadiene and similar aliphatic conjugated dioleilns and refers more particularly to the preparation of elastic, adhesive, and oily products through catalytic polymerization of butadiene.

To those skilled in the art it is well known that many factors enter into the production of useful polymers other than the selection of original raw material. Chief among these factors are: rate of polymerization, temperature, pressure, solvents, and catalyst. The aforesaid conditions are closely interrelated, with the nature of the catalyst probably exerting the most profound influence on the reaction. In the past where diolefln hydrocarbons have been concerned and more particularly in the case of butadiene, emphasis has been placed on' polymerization catalysts' of an alkaline nature. For the polymerization of olefin hydrocarbons, various halogen-containing catalysts of an acidic nature have been proposed such as .aluminum chloride and other compounds of the so-called Friedel-Crafts type, and boron trifluoride. However, these latter catalysts have been variously described as requiring the presence of a promoter, such as traces of water, halogen acids, metals or metallic halides. In general, these halide catalysts have been unsatisfactory in the production of useful polymers from butadiene alone. A specific example is the undesirable powder-like polymer derived from butadiene under the catalytic influence of aluminum chloride.

The principal object of the present invention `is' to provide an improved method for the production of valuable polymers from butadienetype diolens using a series of novel catalytic agents. The nature of the catalysts combined with the procedure for bringing about the Vreactions results in a process for the production of aliphatic conjugated diolen polymers, which is not only an improvement over prior processes,v

but also substantially different from any heretofore described.

Numerous other objcts will hereinafter ap pear.

The accompanying drawing portrays diagrammatically lone form of apparatus which has been found particularly suitable for carrying out .the process of the present invention in a continuous manner. l

The polymerization catalysts employed in accordance with this invention comprise the or.- ganic addition or complex compounds formed in hydric alcohols. The main reaction involved in the absorption of boron fluoride by aliphatic alcohols probably follows the indicated equation:

Reaction in certain instances may be complete with the absorption of one mol of boron uoride per mol of alcohol so that further amounts of boron fluoride are neither absorbed nor retained. In other instances, dependent on the temperature of reaction and the nature of the alcohol, compounds containing rtwo mols `of alcohol per mol of boron nuoride may be formed. With alcohols containing four or more carbon atoms and more especially with secondary and/or tertiary alcocompound produced by the action of boron uoride on an aliphatic alcohol and more particularly compounds of boron fluoride with primary aliphatic alcohols. Furthermore, we have discotered that the rate of reaction and the nature of the resultant polymer can be controlled by maintaining the diolefln concentration in the reaction zone at a low level through the use of a substantially saturated or paranic diluent such as pentane, which is substantially inert under the conditions of polymerization. The process can be carried out as a batch or continuous operation with the latter being preferred in many instances. In accordance with the present invention, an aliphatic conjugated diolefin of the butadiene type (i. e. butadiene or its homologues, such as,

for examplefisoprene, piperylenes, etc., or substitution products of butadiene or its homologues), and preferably butadiene itself, is polymerized by means of a polymerization catalyst consisting of a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol, at a temperature -ranging from about 30 F. to about 120 F., and preferably from about 30 F. to about 100 F., at substantially atmospheric pressure, and inthe presence of a large volume of an inert diluent which is preferably a. solvent reactions of boron fluoride with aliphatic mono- Afor the butadiene, .preferably a solvent for at least the lower liquid polymers of butadiene, and

prefer-amy immiscibie with the catalyst., 1mmiscibility of the solvent or diluent with the liquid catalyst is advantageous because it permits ready separation of catalyst and diluent or polymer solution after reaction, either in a separating zone apart from the reaction zone or in the said reaction zone itself. This separation may conveniently be eiected by allowing layer formation under the influence of gravity or by centrifuging, the liquid catalyst being the heavier. The advantage of this ease of separation due to immiscibility outweighs the advantage of more intimate contact which would be obtained were the diluent a mutual solvent for both the catalyst and the butadiene. Moreover suiiiciently intimate contact for rapid polymerization may be economically and readily obtained by agitating the two immiscible phases in any suitable manner as for example by stirring, by passing through a centrifugal mixing pump, or other contactor.

Another essential feature of our invention is that the concentration of unreacted butadiene, or other dioleln, is maintained throughout the reaction zone and period at a low figure, namely below about volume per cent of the solution or diluent phase, and preferably below about 2 volume per cent downto say about 0.5 volume per cent or lower. This may be effected by using asulcient volume of inert diluent or solvent, or by introducing the gaseous butadiene into the reaction zone, at a suiiiciently low rate and maintaining sulciently rapid conditions of reaction that, at the rate of introduction of butadiene, these limits are not exceeded. Preferably both `of these measures are used.

I sufliciently intimate and extended contact therein,

that the solvent or diluent issuing therefrom contains substantially no unreacted butadiene. In addition conditions are such that the concentration of unreacted butadiene at no point in the reaction zone attains the limits set forth above. In practice, if the concentration of butadiene is kept below these limits at the beginning of the reaction zone, it will necessarily be below these limits in the rest of the reaction zone. A

Preferably the oppositely travelling immiscible liquids are vigorously agitated throughout the major portion of the reaction zone `for intimate' contact 'and rapid reaction. Settling zones in which there is little or no agitation and therefore quiescent opportunity for layer separation, may be advantageously provided at both ends of the reaction zone. Under some circumstances the re action zone may be packed with suitable packing material designed to give intimate contact. Preferably the reaction zone takes the form of a vertical column equipped with a vertical agitator-ine termediate its ends and in which catalyst descends and diluent and butadiene ascend in countercurrent relationship. The catalyst is removed at the bottom and returned to the top while the solution and/or suspension of polymer is removed at the top. Any suspended polymer may be removed and the solution or diluent returned to the bottom of the column. Equilibrium is soon established at the desired economical concentration of polymer in the diluent, whereupon a portion of the solution is withdrawn from the polymer solution circuit and treated in any suitable manner to recover the polymer and solvent or diluent separately therefrom. If desired, though less preferably, the entire dilueni-l or solvent, containing the polymer in solution and/or suspension therein,

leaving the top of the reaction columnmay bel treated to recover all of the polymer therein and the so recovered polymer-free solvent ordiluent recycled to the bottom of the column.

, The dioleiin may be introduced either in gaseous or liquid form, or in the form of a solution in either the fresh or the recycled solvent or diluent, directly into the bottom of the column at a suitable rate. Such a solution may be formed just prior to the point of entry into the bottom of the column.

While it is difficult to fix specific limits for the relative proportions of catalyst, diluent, butadiene and polymer in the reaction zone, the discussion herein will enable those skilled in the art to readily practice the invention without such limits. since the fixing of the other essential operating condition in the manner disclosed herein will automatically determine said relative proportions. However it may be stated that in batch operation the amount of inert solvent or diluent may be as high as about times by weight that of the catalyst. However more catalyst than this may be employed. In a continuous process such as described above, the amount of catalyst may range as high as an amount equal to that of the diluent.

When polymerizing butadiene in accordance with the presenty invention, we prefer to use a temperature ranging from about 30 to about 120 F. or substantially atmospheric temperature. Temperatures of from about 80 F. to about 100 F. are in many cases preferable. As the temperature approaches about 120 F., less desirable polymers are obtained. Above this temperature and especially above 130 F. the product from butadiene is still less suitable for the purpose at hand.

When polymerizing homologues of butadiene, materially different temperatures, than for butadiene, may be found preferable.

While the invention is generally applied to butadiene, which is normally gaseous, it may be ,Y y

applied to homologues thereof, which are nor'- mally liquid, such as isoprene, piperylenes, 2,3- dimethylbutadiene, 2-chlorobutadiene, etc. In suchcase the dioleiin may be introduced to the reaction zone either as such, in the liquid or gaseous formjor in the form of a previously prepared solution in the solvent or diluent employed.

For the preparation of the alcohol-boron uoride addition compounds used as catalytic agents in this process, a convenient procedure consists in. the introduction of boron iluoride into substan tially anhydrous monohydric aliphatic alcohols. By maintaining the reaction temperature below 100 F. and preferably between about 65 and about F., the reaction in most instances with thelower primary alcohols appears to follow the equation previously indicated. Certain commercially available alcohols which are mixtures of isomers, such as the' amyl or octyl alcohols, may absorb from one to two mols of boron uoride per mol o'f alcohol (combination of one-half to one mol of alcohol with one mol of BFa) These boron fluoride alcoholates are stable compounds at the polymerization temperatures employed in this asueto process. Thus, the liquid catalyst used in accordance with the present invention is formed by the reaction of from about one-half to about two moles of BFs with one mol of alcohol.

The production of valuable polymers from butadiene may be carried out by bringing together in a suitable liquid paraflin hydrocarbonreaction medium and diluent, the alcohol-boron fluoride catalyst and relatively small and closely controlled amounts of butadiene hydrocarbon as the substantially pure compound or in mixtures containing a major proportion of the diolen. In such Instances, the polymers formed may be wholly cr partially soluble in the parailln hydrocarbon medium.' Any hydrocarbon-insoluble polymers, of course, separate from the solution and may be removed by suitable means. Additional amounts of butadiene areadded as the polymerization proseeds to maintain optimum concentrations, and the polymer solution may be treated by means such as fractionation or the like to recover the hydrocarbon-soluble material.

Continuous polymerizationl is especially feasible Where reaction conditions favor the formation of hydrocarbon-soluble butadiene polymers. A major problem in conducting polymerization reactions on a commercial scale is the necessity of removing the heat of reaction. The present invention provides a method for conducting such reactions efciently and with good temperature storage tank lo through line II and is introduced i into the top of the reaction chamber where itv passes downward through the ascending stream of the solution of butadiene and polymer in the parain hydrocarbon solvent. Intimate contact between the catalyst and hydrocarbon liquid is maintained by the stirring shaft 'l or its equivalent. Catalyst is removed at the bottom by means of line i2 and pump I3 and returned to storage Ill. Solvent containing the polymerized butadiene is removed continuously through line 8 and recycled by means of line 9 and pump'. After a predetermined viscosity of the polymer solution and/or suspension has been reached, the product is partially diverted via line IDA into a separator IBB while-the remainder is recycled with added make-up solvent being added from '2. Entrained catalyst is separated by gravity in I IlB and relll turned to the catalyst recycle pump I3 via line 20. The supernatant layer of polymer solution passes from separating zone IIIB via line IUC to zone Id where last traces of catalyst are removed from the product stream by .means of a-diluie alkaline solution. The alkali-washed product is subsequently dehydrated by conventional methods in I5. The dryproduct is fed into polymer separator I6 where the solvent is lremoved by distillation with the vapors going overhead into coridenser 2I, where they are condensed to liquid form and thence via lineV Il to solvent storage 2.

The nished polymer is withdrawn from the sep-l aratorl I 5 through line I8. Heat of polymeriza- -phase. non-reactive material to butadiene in the polytion is removed by means cf a selected cooling uid circulated through the cooling jacket I9. A vent line 23, is provided with an automatic pressure release valve 22 in order to maintain substantially atmospheric pressure within the polymerization zone.

Where batch operation is employed the preferred method of contacting the butadiene concentrate and liquid catalyst involves the suspension of said catalyst in a diluent such as selectedl paraffin hydrocarbons. Agitation of the diluent "s essential in order to maintain the catalyst in a nely divided state (as for example to maintain the reaction mixture in the form of an emulsion in which thepcatalyst and diluent are continuously in intimate and extended interfacial contact for rapid reaction). Butadiene, ordinarily in the gaseous state, is introduced beneath the liquid surface and this gradual addition is continued without exceeding the desirable concentration of the unreacted dioleiin until a product of desired characteristics has been produced. The addition of butadiene is so regulated that substantially complete reaction takes place. Temperature control is maintained by means'of 'internal cooling coils. Batch operation may be bons which are the preferred reaction solvents and/or diluents.

In polymerizing butadiene by either batch or continuous operation, we have found that it is exceedingly important to maintain the concentration of butadiene at a low level at all times in order to produce high molecular weight polymers with desirable characteristics. In our process which employs large volumes of unreactive diluent, the concentration of butadiene is always maintained below about 10 per cent and preferably below 2 percent by volume of the diluent The liquid volume ratio of substantially merization mixture thus ranges from 9:1 to 49:1 or more with best results being obtained with the more dilut'e butadiene solutions.

While the polymerization of butadiene according to the present invention is catalyzed by the liquid addition compounds of bor-on iiuoride with aliphatic monohydric alcohols, said addition compounds are not to vbe considered entirely equivalent in their catalytic properties. The choice of a catalyst for theprocess thus may be .dependent on the type of polymeric product desired, and on other economic considerations such as the cost and yield of catalyst frcma specific alcohol.

' The yield of catalyst is ordinarily best with primary aliphatic alcohols, and we often prefer to use primary aliphatic alcohols of 1 to 4 carbon atoms because of the relative purity and availability of alcohols in this group and the good yield of catalyst. With amyl and higher alcohols, the yield of catalyst decreases somewhat with he increasing number of carbon atoms and the c mplexity of the alcohol mixtures. In the case of technicaloctyl alcohol, ,which is a mixture of several octyl alcohols, the catalyst yield is about volume per cent of the alcohol used. y

When the nature ci the polymer product from the various catalysts is considered, exclusive of the effect of polymerization temperatures, the low molecular weight alcohol catalysts appear to vfavor the formation of liquid polymers while the catalyst produced from high molecular weight diene polymers. However, regardless of the catalyst used, only minor variations in activity and reaction rate have been observed, and We do not, therefore, limit ourselves to any particular theory or mode of operation with any specific catalyst composition except as defined and limited by the scope of the present disclosure. We have noted further that the process of the present invention using our catalysts yields a product substantially different from those obtained with boron uoride alone, other conditions Vbeing the same. For example, when the polymerization of butadiene in a hydrocarbon diluent completely saturated with free boron fluoride was attempted, the rate of polymerization was of a distinctly lower order than with the alcohol addition compounds disclosed herein. This resulted in a poor yield of polymer with a great proportion of the butadiene passing through the reaction zone unchanged. The polymer produced under these conditionspossessed generally undef sirable characteristics when compared to products obtained by polymerization in accordance with the present invention with an alcohol -boron fluoride addition compound catalysts. These facts indicate the novel activity and characteristics of the alcohol-boron fluoride compounds as compared to other polymerization catalysts including boron fluoride alone.

The preferred diluents and/orV polymer solvents for this process are the aliphatic parain hydrocarbons which are substantially inert under the polymerizing conditions and which are easily separable from the products of polymerization. These materials may be used in more or less pure form or in mixtures such as may be obtained by the fractionation of natural gasoline or light petroleum fractions of predominantly parailinic nature. Normal pentane, because of its availability and volatility, is often preferred and other paraflins including those of from four to eight or more carbon atoms may be used. The especial advantage of the lower-boiling members is the ease with which they may be flashed or vaporized away from the high-boiling polymers at moderate temperatures. parafns may be employed with goed results.

From the subsequent examples it will be noted that the general procedure of our process affords a maximum of flexibility with respect to operating conditions which influence the nature of the product. Furthermore, variations in temperature and butadiene concentration along with the choice of catalyst result in polymeric products having-substantially diierent properties and uses. For example, polymerization of butadiene at 80 F. in the presence of to 100 or more parts of npentane containing e, small proportion of methanol-boron uoride catalyst produces a viscous transparent polymer which when exposed to air in thin lmsdries to tack-free, non-brittle resins. Polymerization of 3040 F. produces bothliquld and solid polymers, the latter being insoluble in aliphatic hydrocarbons. These solid products are white resilient polymers which disperse and'fswell in'benzene to form extremely viscous solutions and/ or suspensions. On the other hand octanol- `boron fluoride catalyst favors the formation of a greater proportion of pentane-insoluble polymer at both temperature levels mentioned above. l

The amount of catalyst added to any reaction mixture will depend on the total volume of the hydrocarbon polymerization mediumand the emciency of the means for suspending or dispersing 'Il liquid.

However, the Cv, Ca, and higher 5 per cent butadiene concentration was effected at' the catalyst throughout the hydrocarbon liquid. -It is desirable to. have complete and uniform dispersion of catalyst in more or less nely divided condition to provide smooth polymerization. This effect may be accomplished with as little as about one percent by volume of catalyst in the reaction liquid although higher concentrations may be used if desired, particularly in a continuous type polymerization wherein the catalyst is recycled after separation from the hydrocarbon phase.

yOther details relating to the procedure and the advantages of this invention will be described in the following examples which are merely offered by ways of illustration and without limiting the invention.

Example 1 A hydrocarbon gas containing 94 per cent butadiene was polymerized under the influence of a methanol-boron fluoride catalyst in the presence of a large volume of isopentane as the paraln hydrocarbon diluent. The catalyst was prepared by saturating absolute methyl alcohol with boron fluoride at a temperature maintained below F. followed by fractional distillation. The catalyst fraction employed, distilled between Z55-275 F. and presumably consisted of a mixture of monoand dialcoholates of boron fluoride. To 250 cc". of isopentane, 2 cc. of the catalyst was added and maintained in a finely divided state by means of mechanical agitation. 140 g. of gaseous butadiene was introduced beneath the surface of the suspension of catalyst in isopentane at an average rate of 75-80 cc. per minute and the reaction temperature was maintained between 40 and 50. F. Both hydrocarbon soluble and insoluble polymerization products were recovered at the conclusion of the reaction. The catalyst was removed from the reaction products by washing with dilute caustic. After drying the isopentanepolymer solution over solid sodium hydroxide, the

solvent was removed by distillation. The resultant hydrocarbon-soluble polymer was a ,pale yellow, extremely viscous liquid. The hydrocar- J bon-insoluble polymer was a white resilient solid.

A total of 140 g. of butadiene yielded approximately g. of liquid and 40 g. of solid polymer.

Example 2 The polymerization of a hydrocarbon gas of 99 a temperature held substantially at 65 F. in the presence of n-pentane and a boron uoridemethanol catalyst. A catalyst fraction boiling between 275 and 285 F. and consisting essentially of the dialcoholate of boron fluoride wasyused. To

250 cc. of n-pentane, 2 cc. of the methanol-boron fluoride addition compound was added "and maln tained in a state of suspension by means of mechanical agitation. Gaseous butadiene was introduced into the reaction mixture at an average rate of 'I5-80 cc. per minute. At the conclusion of the reaction, both solid and liquid polymerization products were recovered as described in Ex- In this instance the ratio of solid to liquid polymer was considerably less than in the preceding example and modification of physical ample 1.

properties was also apparent. A total of 125 g. of butadiene was polymerized to yield approximately 25 g. of solid and 100 g. of liquid product. The pentane-insoluble polymer wasa white resilient solidsomewhat tougher than the product produced at the lower temperature in isopentane. The soluble product was a transparent viscous decrece Example 3 The polymerization of a hydrocarbon gas of 94 per cent butadiene concentration was carried out substantially as described in Example 2 with the linception of an increase in reaction temperature to 80 F. A very viscous liquid polymer was produced with only a negligible quantity of solid material.

Example 4 The polymerization of a hydrocarbon gas containing 90 per cent butadiene was carried out at a temperature maintained between -80" and 85 F. in the presence of n-pentane and a boron uoridelmethanol catalyst. The catalyst in this instance was the mono-alcoholate of boron iluorideprepared by absorbing 100 mol pex` cent of boron iuoride in absolute methyl alcohol. A countercurrent principle was utilized with n-pentane and gaseous butadiene being fed separatelyinto the bottom oi' a reaction column. The iiow of butadiene was so regulated that a one per cent concentration of unreacted butadiene was maintained in the n-pentane, The catalyst was fed into the top of the column and passed downward through the ascending pentane-butadiene solution. Intimate contact-was maintained in the reaction column bymeans of a stirring shaft. The catalyst was recovered at the bottom of the olunm and recycled for reuse while the pentane polymer solution exiting from thetop of the column was recycled with the continuous addition of butadiene. After the concentration of polymer in the recycled pentane polymer solution reached a value of 5%, a portion of the eilluent solution was bled oiiE from the recirculating system at a rate such as to maintain' this value, and passed to puriiication and recovery steps, in the manner shown the drawing.. A clear viscous liquid polymer was produced by this procedure.

Example 5 Commercial butadiene of 94 per cent purity was catalyst and a butadiene flow rate of 85 cc. per minute. Both pentane-soluble and insoluble polymers were obtained in substantially equal quantities. The soluble polymer was a viscous mucilaginous liquid while the insoluble polymer was recovered in the form of soft crumbs which could be kneaded into a non-sticky resilient mass.

The choice of the inert hydrocarbon diluent will vary with the boiling point of the diolefln being polymerized and the nature of the polymers.

lTherefore, all diluents described herein are not 'diolenns are not equivalents in all aspects of the polymerized in the presence of n-pentane diluent was 1:2. The pentane-soluble polymer was an extremely viscous water-white liquid with the properties of a drying oil. The pentane-insoluble product was a white, soit resilient solid.

Example 6 Commercial butadiene of 94 per cent purity was polymerized in n-pentane in the presence of a catalyst prepared from technical octyl alcohol and boron iluoride. The catalyst was prepared by passing boron iluoride into they octyl alcohol at temperaturesmaintained between 25 and 70 F. until 1.3 mols of boron fluoride had been absorbed per mol ofy alcohol. Side reactions took place with the result that only a 75 per centfyield ci' catalyst was realized. The polymerization was effected at temperatures maintained between '75 and 80 F. in 250 cc. of n-pentane, using 5 cc. of

present invention. Experience in synthetic rubber production has emphasized the differences in behavior of butadiene and the higher diolens in polymerization and in the products obtained. Thus, the proportion of the butadiene polymer soluble in the reaction diluent may be controlled by the herein disclosed reaction controls including temperature. Temperatures for controlling the ratio of soluble to insoluble polymers of Cs and higher aliphatic conjugated diolens may be materially different.

It is to be understood that the invention is not limited to the specific examples which have been offered merely as illustrations and that modifications may be made within the scope of the claims without departing from the spirit of the invention.

We claim:

1. A process for the polymerization of an allphatic conjugated dioleiin which comprises contacting said diolefln with a liquid addition compound of boron nuoride and an aliphatic monohydric alcohol in the presence of a large volume of a parain hydrocarbon as an inert diluent, and maintaining the concentration of unreacted diolefln in the reaction zone at less than about 10 volume per cent of the diluent phase throughout the reaction.

3. A'process for the polymerization of an aliphatic conjugated dioleln which comprises contacting said diolenn with a liquid addition compound of boron iiuoride and an aliphatic monohydric alcohol in the presence of a, large volume of an inert diluent which is a parailln hydrocarbon offrom four to eight carbon atoms.

4. A process for the polymerization of butadiene which comprises contacting said butadiene with a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol in the presence of` a large volume of an inert -diluent which is pentane.

5. The continuous process'of polymerizing an aliphatic conjugated diolefin which comprises establishing two endless flowing circuits of a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol Von the one hand and a solution of said dioleiin in a parailin hydrocarbon as an inert solvent on the other hand, said circuits overlappingy to form a polymerization zone in which the flow is countercurrent and in which said compound -is descending and said solution ascending, continuously introducing unreacted diolen to the bottom of said zone, continuously withdrawing a portion of the solvent stream issuing from the top ofsaid zone, and recovering polymer therefrom.

6. The process of polymerlzing butadiene which comprises ilowing a solution thereof in a large volume of an inert paraihnic solvent upwardly in a polymerization column, flowing a liquid catalyst consisting essentially of an'addition product of boron fluoride and an aliphatic monohydric alcohol downwardly in said column, vigorously agitatto the bottom of said column, introducing solvent to the bottom of said column, withdrawing the balance of said withdrawn solvent phase from the system at a rate equivalent to that at which said fresh butadiene is introduced, recovering butadiene polymer from said balance of said solvent phase, maintaining the temperature in said column between about 30 F. and about 120 F. and the pressure at substantially atmospheric, and maintaining the concentration of unreacted butadiene throughout the reaction zone at below about 10 volume per cent of the solvent phase.

'7. A process for the polymerization of butadiene which comprises contacting same in the presence of a major proportion of a substantially inert paraffin hydrocarbon diluent with a polymerization catalyst consisting of a liquid addition compound of boron uoride and an aliphatic monohvdric alcohol, while maintaining the reaction temperature within the range of about 30 F. to about 120 F. at substantially atmospheric pressure, and maintaining the butadiene concentration below about 10 volume per cent of the hydrocarbon diluent phase.

8. A process for the production of viscous liquid polymers of high molecular weight from butadiene which comprises contacting said butadiene in the presence of suicient parainic hydrocarbon diluent to produce a butadiene concentration in the range of about 0.5 to about 2 volume per cent of the diluent phase with a catalyst consisting of a liquid addition compound of boron fluoride and methanol at temperatures of about 80 to about 100 F.

9. A process for the simultaneous production of hydrocarbon soluble and insoluble polymers from butadiene which comprises contacting butadiene in the presence of sufcient parafilnic hyvdrocarbon diluent to produce butadiene concentrations not exceeding substantially two volume per cent, at temperatures in the range of 50 to 80 F. with a catalyst consisting of an addition compound of boron fluoride and an` aliphatic monohydric alcohol.

l0. A process for the production of high-boiling I polymers of butadiene which comprises continuously introducing butadiene into a stream of a liquid paramnic hydrocarbon solventflowing through a reaction zone counter-current to a stream of a polymerization catalyst consisting of a liquid addition compound of boron uoride and an aliphatic monohydric alcohol whereby butadiene polymers are produced in the hydrocarbon solvent, maintaining the temperature in the reaction zone in the range of 801 to 100 F., and recycling bothcatalyst and polymer solutions to the reaction zone, continuously adding fresh solvent while withdrawing a corresponding amount of polymer solution from the system, and distilling said withdrawn portion of polymer solution after removal of traces of catalyst therefrom to recover butadiene polymers and solvent.

ll; A process for the polymerization of butadiene which comprises contacting butadiene with a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol in the presence of a paraffin hydrocarbon diluent at a temperal ture within the range of about 80 F. to about 100 F. and at substantially atmospheric pressure, and under conditions such that the concentration of unreacted butadiene in the reaction zone is less than about 10 per cent by volume of the hydrocarbon diluent phase. y

l2. A process for the polymerization of butadiene which comprlses contacting butadiene with a liquid addition compound of boron fluoride and` an aliphatic monohydric alcohol containing from about 0.5 to about l mol of boron iiuoride per mol of alcohol, in the presence of a parain hydrocarbon diluent at a temperature within the range of 30 to 120 F. and at substantially atmospheric pressure, and under conditions such that the concentration of unreacted butadiene in the reaction zone is less than about 10 per cent 'by volume of the hydrocarbon diluent phase.

13. A process for the polymerization of an aliphatic conjugated diolefln which comprises contacting said dioleiin with a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol in the presence of a paraiin hydrocarbon diluent at a temperature within the range of about 30F. to about 120 F. and at Sub stantially atmospheric pressure, and under conditions such that the concentration of unreacted dioleiin in the reaction zone is less than about 10 per cent by volume of the hydrocarbon diluent phase.'

14. A process for the polymerization of butadiene which comprises contacting butadiene with a liquid addition compound of boron fluoride and an aliphatic monohydric alcohol in the presence of a paramn hydrocarbon diluent, and maintaining the concentration of unreacted butadiene in the reaction zone at less than 10 per cent by volume of the hydrocarbon diluent phase.

l5. A process for the polymerization of butadiene which comprises contacting butadiene with a liquid addition compound of boron uoride with an aliphatic monohydric alcohol in the presence of a parain hydrocarbon of four to eight carbon atoms per molecule as diluent under conditions such that the concentration of unreacted butadiene in the reaction zone is less than about l0 per cent by volume of the hydrocarbon diluent phase.

16. The process of claim 15 in which the paraffin hydrocarbon is pentane.

WALTER A. SCHULZE. WILLIAM N. AXE. 

